Disclosed are block copolymers of the formula A-b-A (I) or A-b (II), comprising blocks A and b, wherein block A is a hydrophilic polymeric segment comprising polyglycerol and block b is an aromatic hydrophobic polymeric segment. The block copolymers find use as wetting agents in the preparation of porous membranes from aromatic hydrophobic polymers such as polyethersulfone.
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18. A porous membrane comprising an aromatic hydrophobic polymer and a block copolymer of the formula A-b-A (I) or A-b (II), comprising blocks A and b, wherein block A is a hydrophilic polymeric segment comprising polyglycerol and block b is an aromatic hydrophobic polymeric segment.
1. A block copolymer of formula A-b-A (I) or A-b (II), comprising blocks A and b, wherein block A is a hydrophilic polymeric segment comprising polyglycerol and block b is an aromatic hydrophobic polymeric segment selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide.
2. The block copolymer of
##STR00009##
3. The block copolymer of
##STR00010##
4. The block copolymer of
##STR00011##
wherein n is about 10 to about 1000.
6. The block copolymer of
7. The block copolymer of
8. A method of preparing a block copolymer of
(i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups selected from hydroxy, mercapto, and amino groups; and
(ii) carrying out ring opening polymerization of glycidol on the aromatic hydrophobic polymeric segment.
9. The method of
##STR00012##
wherein n is about 10 to about 1000.
11. The method of
12. The method of
13. The method of
14. The method of
15. The method of
17. A method of preparing a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer of
(i) providing a polymer solution comprising a solvent, said aromatic hydrophobic polymer, and said block copolymer;
(ii) casting the polymer solution as a thin film;
(iii) subjecting the thin film to phase inversion to obtain a porous membrane; and optionally
(iv) washing the porous membrane.
19. The porous membrane of
##STR00013##
##STR00014##
wherein n is about 10 to about 1000.
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Aromatic hydrophobic polymers such as polysulfone, polyethersulfone, poly(phthalazine ether sulfone ketone), poly(p-phenylene sulfide), polyether imide, polyimide, polyphenylene oxide, polyphenylene ether, and polyether ether ketone are useful for preparing porous membranes due to their chemical stability, processability, mechanical strength, flexibility, and thermal stability. Since these polymers are generally hydrophobic, membranes prepared from these polymers are hydrophobic, and thus lack desirable surface properties such as wettability, low protein adsorption, thromboresistance, and controlled surface chemical reactivity.
Attempts have been made to improve one or more of the surface properties of membranes made from aromatic hydrophobic polymers. For example, membranes have been treated with high energy radiation or plasma to impart hydrophilicity. In other examples, hydrophilic monomers have been grafted to hydrophobic membrane surfaces. Attempts also have been made to coat the hydrophobic membrane with water soluble polymers such as polyethylene glycol or polyvinyl pyrrolidone. The above attempts for improving properties, particularly hydrophilicity, however, have one or more drawbacks such as lack of reproducibility, lack of stability of the modification, and/or pore clogging.
The foregoing shows that there is an unmet need for hydrophilic membranes formed from aromatic hydrophobic polymers and for a method of imparting hydrophilicity to membranes formed from aromatic hydrophobic polymers.
The invention provides a block copolymer comprising hydrophilic segments which are useful in the preparation of hydrophilic membranes from aromatic hydrophobic polymers. Thus, the present invention provides a block copolymer of formula A-B-A (I) or A-B (II), comprising blocks A and B, wherein block A is a hydrophilic polymeric segment comprising polyglycerol and block B is an aromatic hydrophobic polymeric segment.
The present invention also provides a method of preparing a block copolymer comprising: (i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups; and (ii) carrying out ring opening polymerization of glycidol on the aromatic hydrophobic polymeric segment in the presence of a base.
The present invention also provides hydrophilic porous membranes comprising an aromatic hydrophobic polymer and a block copolymer as described above, and a method of preparing such porous membranes.
The present invention has one or more of the following advantages. It provides for a facile method for tuning the degree of hydrophilicity desired in a porous membrane. Block copolymers of various degrees of hydrophilicity are produced from aromatic hydrophobic polymers. The composition of the block copolymers is readily characterized by well known techniques. The porous membranes prepared using the block copolymers are low in extractables. The block copolymers have strong adhesion to aromatic hydrophobic polymers. The porous membranes are stable to process conditions such as autoclaving, steaming, and isopropanol (IPA) extraction.
In accordance with an embodiment, the invention provides a block copolymer of formula A-B-A (I) or A-B (II), comprising blocks A and B, wherein block A is a hydrophilic polymeric segment comprising polyglycerol (also known as polyglycidol) and block B is an aromatic hydrophobic polymeric segment. Porous membranes comprising a block copolymer of the invention and an aromatic hydrophobic polymer are hydrophilic.
In accordance with an embodiment, the polyglycerol has one or more of the following repeat units:
##STR00001##
In an embodiment, block A comprises of one or more of the following structures:
##STR00002##
In accordance with an embodiment, the aromatic hydrophobic polymeric segment of the block copolymer is selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide, preferably polyethersulfone.
Embodiments of the aromatic hydrophobic polymer segments include polysulfone (PS), polyethersulfone (PES), polycarbonate (PC), polyether ether ketone (PEEK), poly(phthalazinone ether sulfone ketone) (PPESK), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyphenylene oxide (PPO), and polyether-imide (PEI), which have the following structures:
##STR00003##
The number of repeat units, n, within each of the above aromatic hydrophobic segment can be from about 10 to about 1000, preferably from about 30 to about 300, and more preferably from about 50 to about 250.
In accordance with an embodiment, the block copolymer of the invention, where polyethersulfone is the aromatic hydrophobic segment, has the following structure:
##STR00004##
wherein n is about 10 to about 1000, preferably about 50 to 175, and more preferably about 60 to about 100.
Where polysulfone is the aromatic hydrophobic polymer segment, n is about 10 to about 1000, preferably about 30 to about 225, and more preferably about 45 to about 130.
In accordance with an embodiment, block A is present in the copolymer in an amount of about 20% to about 60 mol % and block B is present in an amount of about 30% to about 80 mol %. Preferably, block A is present in an amount of about 40% to about 55 mol % and block B is present in an amount of about 40% to about 60 mol %.
In accordance with an embodiment, the invention also provides a method of preparing the above block copolymer, the method comprising:
(i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups selected from hydroxy, mercapto, and amino groups; and
(ii) carrying out ring opening polymerization of glycidol on the aromatic hydrophobic polymeric segment.
In accordance with an embodiment, the aromatic hydrophobic polymeric segment is selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide, preferably polyethersulfone. The aromatic hydrophobic polymeric segment comprises one or more, preferably one or two, terminal functional groups selected from hydroxy, mercapto, or amino groups.
The functional groups can be provided on the aromatic hydrophobic segments by methods known to those skilled in the art. For example, hydroxy-terminated polyether imide synthesis is described in U.S. Pat. Nos. 4,611,048 and 7,230,066. Thus, for example, hydroxy-terminated polyether imides can be prepared by the reaction of a bis-ether anhydride and a diamine, followed by reaction with an amino alcohol. Illustratively, a hydroxy-terminated polyether imide can be prepared by the reaction of bis(4-(3,4-dicarboxy-phenoxy)phenyl)propane dianhydride and m-phenylenediamine, followed by reaction with p-aminophenol.
Amine-terminated polyether imides can be prepared by the reaction of a bis-ether anhydride and a diamine. Thus, for example, bis(4-(3,4-dicarboxy-phenoxy)phenyl)propane dianhydride and m-phenylenediamine can be reacted to produce an amine terminated polyether imide. See, for example, U.S. Pat. No. 3,847,867.
Hydroxy-terminated PEEK is described in Journal of Polymer Science Part B 2006, 44, 541 and Journal of Applied Science 2007, 106, 2936. Thus, for example, hydroxy-terminated PEEK with pendent tert-butyl groups can be prepared by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with tert-butyl hydroquinone with potassium carbonate as catalyst.
Hydroxy-terminated polycarbonate is described in Journal of Polymer Science: Polymer Chemistry Edition 1982, 20, 2289. Thus, for example, hydroxy-terminated polycarbonate can be prepared by the reaction of bisphenol A and phosgene, with in situ blocking of some of the phenolic groups either prior to or during phosgenation. Trimethylchlorosilane, trifluoroacetic anhydride, or trifluoroacetic acid can be used for the blocking. The blocking group can be removed at the end of the polymerization.
Hydroxy-terminated PPO can be prepared as described in U.S. Pat. No. 3,318,959. Thus, for example, poly-2,6-dimethylphenylene ether can be reacted with sodium hydroxide to obtain a PPO having a hydroxyl content of 2.3 to 3 hydroxyl groups per molecule.
In an embodiment, the aromatic hydrophobic polymeric segment having one or more hydroxy groups is of the formula:
##STR00005##
wherein n is about 10 to about 1000, preferably about 50 to 175, and more preferably about 60 to about 100.
Polyethersulfone is commercially available, for example, as VIRANTAGE VW-10700 from Solvay, with the formula
##STR00006##
which has a GPC molecular weight 21000 g/mol and OH end groups of 210 μeq/g;
as VIRANTAGE VW-10200 from Solvay with the formula
##STR00007##
which has a GPC molecular weight of 44,200 g/mol and OH end groups of 80 μeq/g; and as SUMIKAEXCEL™ 5003PS from Sumitomo with the formula
##STR00008##
which has a reduced viscosity of 0.50 [1% PES dissolved in DMF] and OH end groups in the range of 0.6-1.4 per molecule.
Glycidol or 2,3-epoxy-1-propanol contains one epoxide ring and one hydroxyl group as functional end groups. Both functional end groups are capable of reacting with each other to form macromolecules which are glycerol derivatives. The resulting macromolecules continue to react to form polyglycerol. The opening of the epoxide ring of glycidol is initiated by the nucleophile, i.e., oxide anion, amino group, or sulfide anion, of the aromatic hydrophobic polymeric segment, which is present as the terminal functional group (amino group) or is produced by the reaction of the terminal group (OH or SH) on the aromatic hydrophobic polymeric segment with the base employed in the reaction. In an embodiment, when SH acts as a nucleophile, the use of a base is optional. When an amino group is the nucleophile, then a base is not required.
Any suitable base can be employed, for example, a base selected from potassium carbonate, sodium carbonate, cesium carbonate, sodium tertiary butoxide, potassium tertiary butoxide, tetramethylammonium hydroxide, ammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium carbonate, barium hydroxide, cesium hydroxide, lithium carbonate, magnesium carbonate, magnesium hydroxide, sodium amide, and lithium amide, and combinations thereof.
In accordance with an embodiment, the ring opening polymerization can be carried in a suitable solvent, particularly a polar aprotic solvent. Examples of suitable solvents include N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and mixtures thereof.
The amount of aromatic hydrophobic polymer or glycidol can be present in the polymerization medium at any suitable concentration, for example, from a concentration of about 5% to about 60% or more, preferably about 10% to about 50%, and more preferably about 20% to about 40%, by weight. In an embodiment, the concentration is about 30% by weight.
The ring opening polymerization is conducted such that the ratio of the hydrophobic polymeric segment to glycidol in the reaction mixture is preferably about 1:0.1 to about 1:1.1, more preferably about 1:0.7 to about 1:0.9, and even more preferably about 1:0.8.
The ring opening polymerization is conducted at a suitable temperature, for example, from 25° C. to about 120° C., preferably about 50° C. to about 110° C., and more preferably about 90° C. to 100° C.
The polymerization can be carried out for any suitable length of time, for example, about 1 hr to about 100 hrs or more, preferably about 2 hrs to about 20 hrs, more preferably about 3 hrs to about 10 hrs. The polymerization time can vary depending on, among others, the degree of polymerization desired and the temperature of the reaction mixture.
The polymerization can be stopped by quenching the reaction mixture with an acid. The block copolymer can be isolated from the reaction mixture by precipitation with a nonsolvent, e.g., isopropanol or water. The resulting polymer is dried to remove any residual solvent or nonsolvent.
The block copolymer can be characterized by any suitable analytical technique. For example, the amount of hydrophobic polymeric segment and the amount of the glycidol block (polyglycerol) can be determined by proton NMR spectroscopy.
The present invention further provides a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer as described above. The present invention further provides a method of preparing a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer, the method comprising:
(i) providing a polymer solution comprising a solvent, said aromatic hydrophobic polymer, and said block copolymer;
(ii) casting the polymer solution as a thin film;
(iii) subjecting the thin film to phase inversion to obtain a porous membrane; and optionally
(iv) washing the porous membrane.
The polymer solution for preparing a membrane contains a polymer and a block copolymer as a wetting agent. Typical polymer solutions comprise at least one solvent, and may further comprise at least one nonsolvent. Suitable solvents include, for example, N,N-dimethylformamide (DMF); N,N-dimethylacetamide (DMAC); N-methyl pyrrolidone (NMP); dimethyl sulfoxide (DMSO), methyl sulfoxide, tetramethylurea; dioxane; diethyl succinate; chloroform; and tetrachloroethane; and mixtures thereof. Suitable nonsolvents include, for example, water; various polyethylene glycols (PEGs; e.g., PEG-200, PEG-300, PEG-400, PEG-1000); various polypropylene glycols; various alcohols, e.g., methanol, ethanol, isopropyl alcohol (IPA), amyl alcohols, hexanols, heptanols, and octanols; alkanes, such as hexane, propane, nitropropane, heptanes, and octane; and ketone, ethers and esters such as acetone, butyl ether, ethyl acetate, and amyl acetate; acids, such as acetic acid, citric acid, and lactic acid; and various salts, such as calcium chloride, magnesium chloride, and lithium chloride; and mixtures thereof.
Typical casting solutions contain the polymer in the range of about 10 wt % to about 35 wt % resin, in the range of from about 0.1 to about 10 wt %, preferably about 0.2% to about 2%, and more preferably about 0.3% to about 1% of the hydrophilic block copolymer, in the range of from about 0 to about 90 wt % NMP, in the range of from about 0 to about 90 wt % DMF, and in the range of from about 0 to about 90 wt % DMAC.
Suitable components of casting solutions are known in the art, which may be used as desired. Illustrative solutions comprising polymers, and illustrative solvents and nonsolvents include those disclosed in, for example, U.S. Pat. Nos. 4,629,563; 4,900,449; 4,964,990, 5,444,097; 5,846,422; 5,906,742; 5,928,774; 6,045,899; and 7,208,200.
For example, membrane samples can be prepared through a solution processes involving non-solvent-induced polymer precipitation, either by water vapor diffusion or direct quenching in water. Typically, a solution of the polymer, e.g., PES or PPESK, is prepared first with solvent DMAC or DMAC/NMP, pore former PEG400 and other additives. The solution is applied to a glass plate using a doctor blade with 10˜15-mil space gap, evenly to form a film of polymer dope. The film is then either placed in a chamber with controlled temperature, air velocity and humidity, or directly immersed into a water bath with a preset temperature, allowing some time for the dope to transform into a solid film. The resulting solid film sample is leached in 50˜70% ethanol/water, hot water at a temperature range from 50° C. to 80° C. and then dried in oven at a temperature range from 50-70° C. to afford a sheet of porous polymer membrane.
As an example, a typical formulation consists of PPESK polymer resin at about 15˜25 wt %, solvent (NMP/DMAC) of about 200˜300 phr, wetting polymer agents at a typical range of 5˜25 phr, up to 50 phr. Pore former PEG400 is introduced at a concentration ranging from 50 phr to 100 phr. Other additives at a low percentage 0.5˜3.0% can be used as needed for each individual formulation.
The casting solution is cast as a flat sheet on a glass plate or on a moving substrate such as a moving belt. Alternatively, the casting solution is cast as a hollow fiber.
Phase inversion can be effected by any known method. Phase inversion can include evaporation of the solvent and nonsolvent (dry process); exposure to a nonsolvent vapor, such as water vapor, which absorbs on the exposed surface (vapor phase-induced precipitation process); quenching in a nonsolvent liquid, generally water (wet process); or thermally quenching a hot film so that the solubility of the polymer is suddenly greatly reduced (thermal process).
In an embodiment, phase inversion is effected by exposing the cast solution to a non-solvent vapor, for example, an atmosphere of controlled humidity, following which the cast solution is immersed in a nonsolvent bath such as water bath.
Alternatively, a hydrophobic membrane can be coated with a hydrophilic block polymer. Thus, for example, a solution of the block copolymer is coated on a porous membrane formed from an aromatic hydrophobic polymer, or a porous membrane dipped in a solution of the block copolymer, and optionally, heated, to obtain a hydrophilic modified porous membrane.
As illustrated in
Porous membranes according to embodiments of the invention find use in microfiltration, ultrafiltration, nanofiltration, reverse osmosis, gas separation, pervaporation or vapor permeation, dialysis, membrane distillation, chromatography membranes, and/or forward osmosis and pressure retarded osmosis.
Porous membranes according to embodiments of the invention have a pore size of about 0.05 μm to about 10 μm and find use as microfiltration membranes. Porous membranes according to certain embodiments of the invention have a pore size of about 1 nm to about 0.5 μm and find use as nanofiltration membranes.
Porous membranes according to embodiments of the invention have a critical wetting surface tension (CWST) of about 70 to about 90 dynes/cm or more, for example, 72, 74, 76, 78, 80, 82, 84, or 86 dynes/cm.
Porous membranes according to embodiments of the invention can be used in a variety of applications, including, for example, diagnostic applications (including, for example, sample preparation and/or diagnostic lateral flow devices), ink jet applications, filtering fluids for the pharmaceutical industry, filtering fluids for medical applications (including for home and/or for patient use, e.g., intravenous applications, also including, for example, filtering biological fluids such as blood (e.g., to remove leukocytes)), filtering fluids for the electronics industry (e.g., filtering photoresist fluids in the microelectronics industry), filtering fluids for the food and beverage industry, clarification, filtering antibody- and/or protein-containing fluids, filtering nucleic acid-containing fluids, cell detection (including in situ), cell harvesting, and/or filtering cell culture fluids. Alternatively, or additionally, membranes according to embodiments of the invention can be used to filter air and/or gas and/or can be used for venting applications (e.g., allowing air and/or gas, but not liquid, to pass therethrough). Membranes according to embodiments of the inventions can be used in a variety of devices, including surgical devices and products, such as, for example, ophthalmic surgical products.
In accordance with embodiments of the invention, the porous membrane can have a variety of configurations, including planar, flat sheet, pleated, tubular, spiral, and hollow fiber.
Porous membranes according to embodiments of the invention are typically disposed in a housing comprising at least one inlet and at least one outlet and defining at least one fluid flow path between the inlet and the outlet, wherein at least one inventive membrane or a filter including at least one inventive membrane is across the fluid flow path, to provide a filter device or filter module. In an embodiment, a filter device is provided comprising a housing comprising an inlet and a first outlet, and defining a first fluid flow path between the inlet and the first outlet; and at least one inventive membrane or a filter comprising at least one inventive membrane, the inventive membrane or filter comprising at least one inventive membrane being disposed in the housing across the first fluid flow path.
Preferably, for crossflow applications, at least one inventive membrane or filter comprising at least one inventive membrane is disposed in a housing comprising at least one inlet and at least two outlets and defining at least a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein the inventive membrane or filter comprising at least one inventive membrane is across the first fluid flow path, to provide a filter device or filter module. In an illustrative embodiment, the filter device comprises a crossflow filter module, the housing comprising an inlet, a first outlet comprising a concentrate outlet, and a second outlet comprising a permeate outlet, and defining a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein at least one inventive membrane or filter comprising at least one inventive membrane is disposed across the first fluid flow path.
The filter device or module may be sterilizable. Any housing of suitable shape and providing an inlet and one or more outlets may be employed.
The housing can be fabricated from any suitable rigid impervious material, including any impervious thermoplastic material, which is compatible with the fluid being processed. For example, the housing can be fabricated from a metal, such as stainless steel, or from a polymer, e.g., transparent or translucent polymer, such as an acrylic, polypropylene, polystyrene, or a polycarbonate resin.
The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.
This example illustrates a method of preparing a block copolymer in accordance with an embodiment of the invention.
100 g of BASF E6020 grade polyethersulfone was dissolved in DMAc (250 mL) at 100° C. in a 500 mL flask. Complete dissolution was achieved in 2 hours under vigorous agitation. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (70 mL). The reaction mixture was maintained at 100° C. with constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (90:10 v/v). The precipitate obtained was filtered via a fritted Buchner filter, washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was then dried to yield 140 g of the desired product with 40 mol % of PES and 60 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing another block copolymer in accordance with an embodiment of the invention.
100 g of Sumitomo 5003PS grade polyethersulfone was dissolved in DMAc (250 mL) at 100° C. in a 500 mL flask. Complete dissolution was achieved in 2 hours under vigorous agitation. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. with constant agitation for 5 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (90:10 v/v). The precipitate obtained was filtered via a fitted Buchner filter, washed with water (500 mL) and IPA (250 mL). The resulting white solid was dried to yield 130 g of the desired product with 40 mol % of PES and 60 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (20 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (4 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to yield 105 g of the desired product with 90 mol % of PES and 10 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (15 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (4 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 107 g of the desired product with 90 mol % of PES and 10 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (25 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (5 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 107 g of the desired product with 85 mol % of PES and 15 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (35 mL). The reaction mixture was maintained at 100° C. under constant agitation for 5 hours. The reaction mixture was quenched by the addition of acetic acid (5 mL) and allowed to cool down to room temperature. The resulting product was then precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 110 g of the desired product with 80 mol % of PES and 20 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (50 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (8 mL) and allowed to cool down to room temperature. The product obtained was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 110 g of the desired product with 67 mol % of PES and 33 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (60 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction was quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The product obtained was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20 v/v). The precipitate obtained was filtered via a fitted Buchner filter, and washed with DI water (250 mL) and IPA (500 mL). The resulting solid was dried to obtain 110 g of the desired product with 53 mol % of PES and 47 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (80 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20, v/v). The precipitate obtained was filtered via a fritted Buchner filter and washed with DI water (500 mL) and IPA (500 mL). The resulting solid was dried to obtain 120 g of the desired product with 35 mol % of PES and 65 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing a block copolymer which is partially soluble in water.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA. The precipitate obtained was then filtered via a fritted Buchner filter and washed with DI water (500 mL) and IPA (500 mL). The resulting solid was dried to obtain 110 g of the desired product with 25 mol % of PES and 75 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing a block copolymer which is soluble in water.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (150 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA. The precipitate obtained was filtered via a fritted Buchner filter and washed with DI water (500 mL) and IPA (500 mL). The resulting solid was dried to obtain 130 g of the desired product with 10 mol % of PES and 90 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (40 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (4 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to yield 105 g of the desired product with 85 mol % of PES and 15 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (50 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (6 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 105 g of the desired product with 80 mol % of PES and 20 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (60 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was then quenched by the addition of acetic acid (8 mL) and allowed to cool down to room temperature. The resulting product was precipitated by slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 110 g of the desired product with 70 mol % of PES and 30 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (70 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was then quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20 v/v). The resulting precipitate was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 115 g of the desired product with 55 mol % of PES and 45 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (120 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20 v/v). The precipitate obtained was filtered via a fritted Buchner filter and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 140 g of the desired product with 30 mol % of PES and 70 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing a block copolymer which is partially soluble in water.
100 g of BASF E6020 grade polyethersulfone was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. The complete dissolution was achieved in 2 hours under vigorous agitation. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (110 mL). The reaction mixture was maintained at 100° C. and constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (90:10 v/v). The precipitate obtained was filtered via a fitted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was dried to obtain 150 g of the desired product with 20 mol % of PES and 80 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing another block copolymer which is partially soluble in water.
100 g of BASF E7020 grade polyethersulfone was dissolved in DMAc (300 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. and constant agitation for 12 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (80:20 v/v). The precipitate obtained was filtered via fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was dried to obtain 150 g of the desired product with 30 mol % of PES and 70 mol % of glycidyl as determined by proton NMR.
This example illustrates a method of preparing yet another block copolymer in accordance with an embodiment of the invention.
100 g of Sumitomo 5400P grade polyethersulfone was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. under constant agitation for 12 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (80:20 v/v). The precipitate obtained was filtered via a fitted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was dried to obtain 140 g of the desired product with 35 mol % of PES and 65 mol % of glycidyl as determined by proton NMR.
This example illustrates some of the properties of the block copolymers in accordance with an embodiment of the invention.
TABLE 1
Properties of Block Copolymers
PES segment (mol
Pg segment (mol
PES MW
% by NMR)
% by NMR)
Water Solubility
PES-22KD
85
15
No
PES-22KD
80
20
No (Hydrophilic)
PES-22KD
70
33
No (Hydrophilic)
PES-22KD
53
47
No (Hydrophilic)
PES-22KD
25
75
Yes
PES-45KD
80
20
No (Hydrophilic)
PES-45KD
70
30
No (Hydrophilic)
PES-45KD
55
45
No (Hydrophilic)
PES-45KD
48
52
No (Hydrophilic)
This example illustrates the preparation of porous membranes in accordance with an embodiment of the invention.
Block copolymers (PES-Pg) prepared in Examples 1 and 2 were employed as wetting agents in preparing porous PES membranes. The wetting agent was employed at 6.9 phr of the PES. The compositions of the membrane casting solutions are set forth in Table 2 below along with that of the control membrane where PVP K-90 was employed as the wetting agent. The casting solutions were clear as indicated in the Comment.
TABLE 2
PES Membrane Formulations Prepared Using PES-Pg
from Examples 1 and 2
Control
PES-Pg
PES-Pg
PES-Pg
PES-Pg
%
%
%
%
%
PEG
64.5
64.5
63.6
64.9
64.5
H2O
3.0
3.0
3.0
3.0
3.0
DMF
10.0
10.0
10.0
10.0
10.0
NMP
7.6
7.6
7.6
7.6
7.6
PES
13.0
13.0
13.0
13.0
13.0
Glycerin
1.0
1.0
1.0
1.0
1.0
Wetting
0.9
0.9
1.80
0.45
0.9
Agent
PVP K90
Example 1
Example 1
Example 1
Example 2
Comment
Clear Mix
Clear Mix
Clear Mix
Clear Mix
Clear Mix
The membrane casting solutions were cast using vapor-induced phase separation process, with a casting temperature of 43° C., relative humidity of 75%, and dry bulb of 25° C. No formulation defects were observed. Sumitomo PES was used.
Physical properties and CWSTs were measured on the dried membranes and are set forth in Table 3. Samples of the membrane were also tested for IPA extractables. 6 discs of 47 mm diameter were dried for 1 hour at 80° C. and Soxhlet extracted with IPA for 3 hours followed by a final 1 hour dry cycle at 80° C. The % extractables were calculated. The CWSTs were again measured after the IPA extraction and are set forth in Table 3.
TABLE 3
Physical Properties and CWST of Porous Membranes
0.90%
1.8%
0.90%
0.45%
0.9%
Sample
PVP K90
PES-Pg
PES-Pg
PES-Pg
PES-Pg
(Mix ID)
Control
Example 1
Example 1
Example 1
Example 2
Thick (mils)
6.2
5.45
5.65
5.4
6.6
Water Flow
11.4
15.6
14.3
16.1
14.2
Rate
(ml/min/cm2)
Bubble Point
82.33
80.44
79.51
76.18
64.86
(psi)
CWST
87
90
86
77
87
(dynes/cm)
IPA
2.24
1.09
1.04
1.04
1.03
Extractables
(%)
This example illustrates the preparation of additional porous membranes in accordance with an embodiment of the invention.
Block copolymers (PES-Pg) prepared in Examples 2 and 7 were employed as wetting agents in preparing porous PES membranes. The wetting agent was employed at 6.9 phr of the PES. The compositions of the membrane casting solutions are set forth in Table 4 and the membrane casting conditions are set forth in Table 5.
TABLE 4
Compositions of Membrane Casting Solutions
Control
Example 7
Example 7
Example 2
Example 2
Components
%
%
%
%
%
PEG-400
66.40
66.40
64.40
66.40
64.40
PES
14.0
13.0
13.0
13.0
11.0
(Sumitomo)
Example 7
—
1.0
3.0
—
—
Example 2
—
—
—
1.0
3.0
RO Water
2.0
2.0
2.0
2.0
2.0
DMF
11.0
11.0
11.0
11.0
11.0
NMP
6.6
6.6
6.6
6.6
6.6
TABLE 5
Membrane Casting Conditions
Condition
Setting
Mix Temperature (° C.)
38
Casting Thickness (mils)
12
Casting Plate Temperature (° C.)
43
Chamber Plate Temperature (° C.)
38
Dry Bulb (° C.)
25
RH (%)
75
Air Velocity (fps)
5.0
Leach
ambient water/ethanol-water
(1:1)/hot water (40° C.)
Dry (° C.)
60
0.2 μm diameter porous membranes were produced and they did not contain any membrane defects, indicating compatibility of the copolymer with the base PES. Some of the properties of the membranes are set forth in Table 6. The block copolymer additive increased the CWST of the membranes of the invention compared to the control membrane. The block copolymer from Example 2 had a greater molecular weight than the one from Example 7, and resulted in a significant increase in the CWST. The membrane prepared with the block copolymer of Example 2 had a significantly high water flow rate.
TABLE 6
Properties of Porous Membranes
CWST
Water
CWST
(dynes/cm;
Bubble
Water
(dynes/cm;
145° C. Dry
Point
Flow Rate
CWST
145° C. Dry
Heat for
(water;
(ml/min @ 0.7
Thickness
(dynes/cm
Heat for 2
3 hours +
Membrane
Mixture
Formulation
psi)
bar: 10 psi)
(mils)
as cast)
hours )
IPA ext)
Visual
Visual
Control
50
23
4.8
70
69
69
No Defects
clear
Ex. 7
51
31
5.0
76
76
76
No Defects
clear
Ex. 7
52
29
4.6
79
76
76
No Defects
clear
Ex. 2
43
51
5
90
86
87
No Defects
clear
Ex. 2
53
46
5
90
86
87
No Defects
clear
SEM images of the membranes indicate that the PES-Pg membranes have a typical PES membrane porous structure, which is required for membrane flow, strength, and filter-life performance.
This example illustrates the pore sizes of porous membranes as a function of the amount of hydrophilic block copolymer employed in the preparation of porous membranes in accordance with an embodiment of the invention.
Casting solutions containing 12.1% polyethersulfone resin, 22.5% t-amyl alcohol, in NMP solution, and one of the following: 0.3%, 0.6%, 1%, or 2% hydrophilic block copolymer, were prepared. The solution was deposited onto a Mylar sheet or a textured substrate support as a thin film. Phase inversion was initiated based on the air gap. Air velocity was controlled over the gap by controlling the speed of the fan. Phase inversion was completed by immersing it in a nonsolvent bath, followed by rinse in RO water and oven drying. The results obtained are set forth below in Table 7 and show that very small concentrations of the hydrophilic block copolymer, e.g., at 0.3%, high CWST's are obtained. At 0.3% and 0.6% concentrations of the hydrophilic block copolymer, the pore size obtained was 10 nm.
TABLE 7
Membrane Casting Parameters and Properties of Membranes
Wet Water
Hydrophilic
Flow
Block
Quench
Casting
(ml/min @
CWST
Copolymer,
temp
speed
10 psi for 90
Pore Size
(dynes/
% by wt
Air Gap
(° F.)
(fpm)
mm disc)
(nm)
cm)
Control
0
1 inch
78
12
430
10
~55
PES
media
EXP 1
0.3
1 inch
78
12
296
10
>72
EXP 2
0.6
1 inch
78
12
290
10
>76
EXP 3
1
1 inch
68
12
275
<10
>76
EXP 4
2
1 inch
68
12
250
<10
>76
This example illustrates the preparation of porous membranes comprising a blend of PPESK and PES-Polyglycerol (PES-Pg) as wetting agent.
A casting solution containing a PPESK resin at 15 wt %, solvent NMP/DMAc (v/v) at 300 phr, the PES-Pg of Example 2 at 10 phr was prepared and cast as a 15 mil thick film at 28° C., air temperature 32° C., relative humidity 72%. Water bath temperature was set at 80° C. The dope was placed in an environmental chamber for 15 seconds and immersed in water at room temperature. The membrane had a CWST of 76 dynes/cm. The morphology of the membrane was characterized by SEM.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Ait-Haddou, Hassan, Onyemauwa, Frank
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